CN109053383B - Method and catalyst for efficiently alcoholysis of polycarbonate under mild condition - Google Patents
Method and catalyst for efficiently alcoholysis of polycarbonate under mild condition Download PDFInfo
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- CN109053383B CN109053383B CN201810614495.5A CN201810614495A CN109053383B CN 109053383 B CN109053383 B CN 109053383B CN 201810614495 A CN201810614495 A CN 201810614495A CN 109053383 B CN109053383 B CN 109053383B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
- C07C37/0555—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group being esterified hydroxy groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0282—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aliphatic ring, e.g. morpholinium
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Abstract
The invention relates to a method and a catalyst for high-efficiency alcoholysis of Polycarbonate (PC) under mild conditions, wherein the method takes DBU proton type ionic liquid as the catalyst, takes methanol, ethanol, propanol, isopropanol, n-butanol or isobutanol as an alcoholysis reactant, and comprises the following steps of: 2-8, the dosage of the catalyst is 0.3-10 mol% of the molar weight of the reactant (PC + alcohol), and the reaction temperature is 50-120oAnd C, alcoholysis of the polycarbonate under the condition that the reaction time is 0.5-5 h. The method has the advantages of cheap and easily-obtained catalyst, simple preparation, high catalytic activity, mild alcoholysis reaction conditions, easy separation of the catalyst and the product, and recycling.
Description
Technical Field
The invention relates to a novel method for efficiently alcoholysis of polycarbonate under mild conditions and a catalyst thereof, belonging to the fields of clean catalysis and solid waste recycling.
Technical Field
Polycarbonate (PC), named 2, 2-bis (4-hydroxyphenyl) propane polycarbonate, is also called bisphenol A (BPA) type polycarbonate, is a linear high molecular compound with a carbonate group in a molecular main chain, and has good optical characteristics, mechanical properties, flame retardant property and high temperature resistance. As one of five engineering plastics, the PC is widely applied to the fields of building boards, medical instruments, aerospace, electronic and electrical appliances, optical lenses and the like, and has wide market prospect. In recent years, with the rapid increase of the production and sale of PC materials, the amount of waste PC generated is also increased year by year. Because the size is large and the material is difficult to degrade under natural conditions, the material not only can cause important influence on the ecological environment in the long term, but also is huge in resource waste. Therefore, people pay attention to recycling of waste PC materials.
The traditional method for recycling the waste PC materials mainly adopts a physical recycling method, namely, the novel recycled materials are prepared through technological processes of melting, purification or modification and the like, but the mechanical and physical properties of the processed novel plastic products are reduced. The chemical recovery method is used as an alternative strategy and shows great development potential, namely, the waste PC is depolymerized into a low-molecular-weight compound or monomer BPA by a chemical method, and the compound or monomer BPA is refined and then is used as the raw material of the PC or used for preparing other plastic products, so that the resource recycling is realized. The chemical method mainly comprises thermal cracking, hydrolysis, ammonolysis, alcoholysis and the like, wherein the selectivity of a monomer BPA obtained by the thermal cracking method is poor, and a large amount of byproducts are generated; hydrolysis and ammonolysis processes are usually operated at high temperature and high pressure, require catalysts such as strong inorganic acids or strong bases, not only corrode equipment, but also accompany with greenhouse gas CO2And (4) discharging. However, the alcoholysis strategy for recovering the waste PC material can not only prepare the monomer BPA with high selectivity, but also by-produce novel high-added-value chemical products (organic carbonate), thereby showing obvious advantages.
The existing catalyst used for alcoholysis of PC is reported to be mainly inorganic strong base, the catalyst is difficult to separate from the product, and the catalyst cannot be effectively recycled and reused, and has the disadvantages of equipment corrosion, environmental pollution and the like. The ionic liquid has unique physical and chemical properties of low vapor pressure, high stability, strong dissolving capacity, adjustable pH value and structure and the like, and is widely applied to a plurality of fields as a novel green solvent and a catalyst. Until now, researches on the adoption of alkaline ionic liquid to catalyze the alcoholysis of PC have been reported. However, the reported ionic liquids are generally synthesized by a two-step method, and a large amount of salt and solvent are introduced in the process involving anion exchange, and the synthetic process of the ionic liquids cannot meet the environment-friendly property. Meanwhile, the ionic liquid has high synthesis raw material cost, and the synthesis process usually needs long-time condensation and reflux, so that the ionic liquid is expensive and the synthesis energy consumption is high; more importantly, the reported ionic liquid catalyst has large dosage and harsh reaction conditions, and the industrialization process of the ionic liquid catalyst is hindered from the aspects of catalytic process and manufacturing cost. Therefore, for alcoholysis solid waste PC materials, the design and development of novel ionic liquids should focus on selecting safe and cheap synthetic raw materials, simple synthetic process, and realizing high efficiency catalytic alcohol depolymerization carbonate under mild conditions with low catalyst usage. The environment-friendly ionic liquid is used as a novel catalyst for PC alcoholysis, so that the ionic liquid is recycled, the defects of the traditional process are overcome, the problems of equipment corrosion and pollution are obviously improved, and the method has an important significance in realizing chemical recycling of waste PC materials.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for synthesizing a catalyst, which is simple, high in stability, recyclable, and capable of efficiently and cleanly depolymerizing carbonic ester (PC) by alcohol under the conditions of mild and low catalyst dosage. The PC alcoholysis reaction equation is as follows:
in order to solve the technical problems, the invention provides an ionic liquid catalyst for high-efficiency alcoholysis of polycarbonate under mild conditions, which is synthesized by adopting a one-step acid-base neutralization method and is composed of DBU cations and imidazole anions with different substituents, and has the following structural general formula:
the invention provides a method for efficiently alcoholysis of polycarbonate under mild conditions, which comprises the following steps:
(1) adding a reactant PC, a reactant alcohol and an ionic liquid catalyst into a reactor in sequence, wherein the molar ratio of PC to alcohol is 1: 2-8, wherein the ionic liquid accounts for 0.3-10 mol% of the molar content of the reactants (PC + alcohol);
(2) heating the reaction system in an oil bath to 50-120 ℃, and keeping the temperature for 0.5-5 h;
(3) after the reaction is finished, cooling the reactor to room temperature through ice-water bath, filtering, washing and drying a filter cake, weighing, and calculating the PC conversion rate;
(4) taking the filtrate, carrying out reduced pressure rotary evaporation to separate out excessive alcohol and a byproduct carbonate, adding ether and water to respectively extract a product BPA and an ionic liquid, carrying out reduced pressure rotary evaporation on an upper ether phase to obtain a high-purity product BPA, and calculating the yield of the product BPA; and (5) carrying out reduced pressure rotary evaporation and vacuum drying on the lower-layer water phase to recover the ionic liquid, and testing the reusability of the ionic liquid.
As a further optimization of the invention, the ionic liquid structure in the step (1) is [ HDBU][2-NitrIm]: R1= R2 = H, R3 = NO2, [HDBU][Im]: R1 = R2 = R3 = H, [HDBU][2-PhIm]: R1 = R2 = H, R3= Ph or [ HDBU][4-MeIm]: R1 = R3 = H, R2 =CH3Or a mixture of any two of them.
As a further optimization of the present invention, the molar ratio of the reactants PC and alcohol in step (1) is 1: 4-6, wherein the ionic liquid accounts for 0.8-4 mol% of the molar content of the reactants.
As a further optimization of the method, the reaction temperature in the step (2) is 50-70 ℃, and the reaction time is 1-4 h.
As a further optimization of the invention, the reactant alcohol in the step (1) is one of methanol, ethanol, propanol, isopropanol, n-butanol or isobutanol.
As a further optimization of the invention, the reactant alcohol in the step (1) is methanol.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in: the catalyst for efficient alcoholysis of polycarbonate under mild conditions is DBU proton type ionic liquid, is simple and easy to obtain, and can be prepared by one-step neutralization reaction at room temperature and in the absence of solvent; the DBU proton type ionic liquid is used as a catalyst and applied to the PC alcoholysis reaction, so that the reaction condition is mild, the catalyst consumption is low, and the catalytic efficiency is high; the product separation and the ionic liquid regeneration can be realized through the extraction process, and the recycling of the ionic liquid is easy to realize. Compared with the traditional method, the method overcomes the defects that the reaction is carried out under the conditions of strong acid and strong alkali, and obviously improves the problems of equipment corrosion and wastewater discharge; DBU proton type ionic liquid is selected as a catalyst, the dosage of the DBU proton type ionic liquid is small, the catalytic activity and the catalytic efficiency are obviously improved, the reaction condition is mild, and the energy consumption is reduced; the reaction system can avoid the dissolution of additional organic solvent to PC, and simplify the operation process; and the ionic liquid has better recycling availability, is an environment-friendly production process and has good industrial application prospect.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, and the following examples are only illustrative of the present invention and are not intended to limit the present invention.
Example 1
Taking reactants of PC and methanol, and catalyst (HDBU)][Im]A stainless steel autoclave equipped with a stirrer and a thermometer was charged successively, wherein PC 15.7 mmol (4.0 g) and the molar ratio of PC to methanol was 1: 5, [ HDBU][Im]Accounting for 3.4 mol percent of the molar content of the reactants; the reaction system was oil-bath heated to 50 deg.CoC, keeping for 4 hours; after the reaction is finished, the reaction kettle is cooled to room temperature through an ice water bath, the reaction liquid is subjected to filtering, washing and extracting steps to prepare a pure product BPA, and the PC conversion rate is calculated to be 100%, and the yield of the BPA is calculated to be 96%.
Example 2
Taking reactants of PC and methanol, and catalyst (HDBU)][Im]A stainless steel autoclave equipped with a stirrer and a thermometer was charged successively, wherein PC 15.7 mmol (4.0 g) and the molar ratio of PC to methanol was 1: 5, [ HDBU][Im]Accounting for 1.7 mol percent of the molar content of the reactants; the reaction system was oil-bath heated to 70 deg.CoC, keeping for 2 h; after the reaction is finished, the reaction kettle is cooled to room temperature through an ice water bath, the reaction liquid is subjected to filtering, washing and extracting steps to prepare a pure product BPA, the PC conversion rate is calculated to be 100%, and the yield of the BPA is calculated to be 98.4%.
Example 3
Taking reactants of PC and methanol, and catalyst (HDBU)][Im]A stainless steel autoclave equipped with a stirrer and a thermometer was charged successively, wherein PC 15.7 mmol (4.0 g) and the molar ratio of PC to methanol was 1: 5, [ HDBU][Im]Accounting for 0.8 mol percent of the molar content of the reactants; heating the reaction system to 80 deg.C in oil bathoC, keeping for 1 h; after the reaction is finished, the reaction kettle is cooled to room temperature through an ice water bath, the reaction liquid is subjected to filtering, washing and extracting steps to prepare a pure product BPA, the PC conversion rate is calculated to be 100%, and the yield of the BPA is calculated to be 94.3%.
Example 4
Taking reactants of PC and methanol, and catalyst (HDBU)][2-MeIm]A stainless steel autoclave equipped with a stirrer and a thermometer was charged successively, wherein PC 15.7 mmol (4.0 g) and the molar ratio of PC to methanol was 1: 5, [ HDBU][2-MeIm]Accounting for 1.7 mol percent of the molar content of the reactants; the reaction system was oil-bath heated to 70 deg.CoC, keeping for 1.5 h; after the reaction is finished, the reaction kettle is cooled to room temperature through an ice water bath, the reaction liquid is subjected to filtering, washing and extracting steps to prepare a pure product BPA, the PC conversion rate is calculated to be 100%, and the yield of the BPA is calculated to be 92.1%.
Example 5
Taking reactants of PC and methanol, and catalyst (HDBU)][2-PhIm]A stainless steel autoclave equipped with a stirrer and a thermometer was charged successively, wherein PC 15.7 mmol (4.0 g) and the molar ratio of PC to methanol was 1: 5, [ HDBU][2-PhIm]Accounting for 1.7 mol percent of the molar content of the reactants; the reaction system was oil-bath heated to 70 deg.CoC, keeping for 1 h; after the reaction is finished, the reaction kettle is cooled to room temperature through an ice-water bath, the reaction liquid is subjected to filtering, washing and extracting steps to prepare a pure product BPA, and the PC conversion rate is calculated to be 99.0%, and the yield of the BPA is calculated to be 93.5%.
Example 6
Taking reactants of PC and methanol, and catalyst (HDBU)][2-iPrIm]A stainless steel autoclave equipped with a stirrer and a thermometer was charged successively, wherein PC 15.7 mmol (4.0 g) and the molar ratio of PC to methanol was 1: 5, [ HDBU][2-iPrIm]Accounting for 1.7 mol percent of the molar content of the reactants; the reaction system was oil-bath heated to 70 deg.CoC, keeping for 2 h; after the reaction is finished, cooling the reaction kettle to room temperature through ice-water bath, and filtering, washing and extracting reaction liquid to obtain the catalystPure BPA, calculated as 100% PC conversion and 97.8% BPA yield.
Example 7
Taking reactants of PC and methanol, and catalyst (HDBU)][4-MeIm]A stainless steel autoclave equipped with a stirrer and a thermometer was charged successively, wherein PC 15.7 mmol (4.0 g) and the molar ratio of PC to methanol was 1: 5, [ HDBU][4-MeIm]Accounting for 1.7 mol percent of the molar content of the reactants; the reaction system was oil-bath heated to 70 deg.CoC, keeping for 1 h; after the reaction is finished, the reaction kettle is cooled to room temperature through an ice water bath, the reaction liquid is subjected to filtering, washing and extracting steps to prepare a pure product BPA, the PC conversion rate is calculated to be 100%, and the yield of the BPA is calculated to be 94.0%.
Examples 8 to 12
The specific experimental conditions and procedures were the same as in example 2 except that methanol was changed to ethanol, propanol, isopropanol, n-butanol or isobutanol, respectively, and the results are shown in table 1.
Examples 13 to 17
The experimental conditions and procedures were the same as in example 2 except that the catalyst [ HDBU ] [ Im ] was changed to the ionic liquid recovered in example 2, and 5 cycles of experiments were carried out under the same conditions, and the results are shown in Table 2.
Example 18
The following table 3 shows that the novel DBU proton ionic liquid provided by the present invention shows significant advantages in catalytic reaction conditions and activity in comparison with a series of catalysts reported in the literature.
Claims (8)
1. The application of the ionic liquid as the catalyst for the high-efficiency alcoholysis of polycarbonate under the mild condition is characterized in that the ionic liquid is composed of DBU cations and imidazole anions with different substituents, and the structural general formula of the ionic liquid is as follows:
2. a method for efficiently alcoholysis of polycarbonate under mild conditions is characterized by: the method comprises the following steps:
(1) taking a reactant PC, a reactant alcohol and the catalyst ionic liquid as described in claim 1, and sequentially adding the reactants PC and the reactant alcohol into a reactor, wherein the molar ratio of the PC to the alcohol is 1: 2-8, wherein the ionic liquid accounts for 0.3-10 mol% of the molar content of the reactants;
(2) heating the reaction system to 50-80 ℃, and keeping for 0.5-5 h;
(3) after the reaction is finished, cooling the reactor to room temperature, and filtering;
(4) and (3) taking the filtrate, carrying out reduced pressure rotary evaporation to separate out excessive alcohol and a byproduct carbonate, adding diethyl ether and water to extract a product BPA and an ionic liquid respectively, and carrying out reduced pressure rotary evaporation on an upper diethyl ether phase to obtain a high-purity product BPA.
3. The method of claim 2, wherein the alcoholysis of the polycarbonate is conducted under mild conditions, and wherein: the ionic liquid has a structure of [ HDBU][2-NitrIm]: R1 = R2 = H, R3 = NO2, [HDBU][Im]: R1 = R2 = R3= H, [HDBU][2-PhIm]: R1 = R2 = H, R3= Ph or [ HDBU][4-MeIm]: R1 = R3 = H, R2 =CH3Or a mixture of any two of them.
4. The method of claim 2, wherein the alcoholysis of the polycarbonate is conducted under mild conditions, and wherein: the ionic liquid has a structure of [ HDBU][Im]: R1 = R2 = R3 = H。
5. A method for efficient alcoholysis of polycarbonate under mild conditions as in claim 2 or 3 wherein: the molar ratio of the reactants PC and the alcohol in the step (1) is 1: 4-6, wherein the ionic liquid accounts for 0.8-4 mol% of the molar content of the reactants.
6. A method for efficient alcoholysis of polycarbonate under mild conditions as in claim 2 or 3 wherein: the reaction temperature in the step (2) is 50-70 ℃, and the reaction time is 1-4 h.
7. A method for efficient alcoholysis of polycarbonate under mild conditions as in claim 2 or 3 wherein: the reactant alcohol in the step (1) comprises one of methanol, ethanol, propanol, isopropanol, n-butanol or isobutanol.
8. A method for efficient alcoholysis of polycarbonate under mild conditions as in claim 2 or 3 wherein: the reactant alcohol in the step (1) is methanol.
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| CN101407450A (en) * | 2008-05-14 | 2009-04-15 | 青岛科技大学 | Chemical recovery method for waste polycarbonate material |
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